JP2021523275A - 強化ポリエステル構造部材 - Google Patents
強化ポリエステル構造部材 Download PDFInfo
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- JP2021523275A JP2021523275A JP2020563638A JP2020563638A JP2021523275A JP 2021523275 A JP2021523275 A JP 2021523275A JP 2020563638 A JP2020563638 A JP 2020563638A JP 2020563638 A JP2020563638 A JP 2020563638A JP 2021523275 A JP2021523275 A JP 2021523275A
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- polyester
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- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
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- 238000002425 crystallisation Methods 0.000 claims description 58
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- 239000003365 glass fiber Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 26
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
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- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 7
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
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- 239000004927 clay Substances 0.000 claims description 3
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 11
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
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- YJLVKRVGSARISS-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphite Chemical compound CC1=CC=CC(C)=C1OP(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C YJLVKRVGSARISS-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
【選択図】図1
Description
物品を、30〜40wt%の細断ガラス繊維を有するPBTとPETとの組み合わせから、実施例1〜5および比較例1のように調製した(表3)。PETのPBTに対する重量比は、33:67から57.8:42.2まで変化させた。ブレンドは、核生成用の小粒径タルクならびに結晶成長および離型用のEBSワックス滑剤をさらに含んでいた。組成を表3に示し、構成成分は重量パーセント(wt%)で表した。
物品を、35〜50wt%の細断された長ガラス繊維を有するPBTとPETとの組み合わせから、実施例9および10のようにそれぞれ調製した。PETのPBTに対する重量比は35:65であった。物品は、カーボンブラック、ヒンダードフェノール抗酸化剤、オレフィンワックス、およびDPIDPをさらに含んでいた。組成を表7に示し、構成成分は重量パーセント(wt%)で表した。
一般的手順は、10〜12マイクロメートルの繊維織物材料の多方向織りを含むガラス繊維織物を、実施例11のPET−PBTの極低温機械式粉砕によって調製された350ミクロンの粉砕粉末に接触させることを含む。粉砕粉末を数プライ(ply)の織布に接触させて(約320℃)セミプレグを形成し、移動ベルトを使用して圧力下で加熱することによって圧密化し、次いで冷却してPET−PBTガラス織布積層体を形成した。ガラス繊維を、溶融PET−PBT樹脂で実質的に湿潤させ、被包した。
複合多室チャンネル(CMCC)部品を、実施例6、7、または8の組成物を使用して成形した。この試験部品は、長さ41cm、高さ5cm、および幅5cmの寸法を有していた。部品の上部および底部は、開放された六角形および台形のチャンネルであった。内室は、切れ目ない2つの対向側面を接続する20の交互の列から構成されていた。この列は、2つの六角形が中央の六角形と交互に共通の辺を有し、その中央の六角形が、切れ目ない対向側面に融合した2つの台形を有するものであった。この部品の端部の列には中央の六角形があり、その六角形の対向側に2つの台形が融合していた。これらの六角形は、25mmの長さおよび20mmの幅を有しており、その長軸は、複合チャンネル部品の長さに揃えられていた。六角形および台形の壁厚は、2.0〜3.5mmであり、中間の3つの六角形/台形の列の壁の方が厚かった。この部品は、高さ5cmおよび厚さ3mmの、切れ目ない対向側面の間に交互に角のある(W/M状)接続部を有する、正方形の断面周囲を有していた。
実施例12〜17のPET−PBT−GF積層体は、細断ガラス、長ガラス、または細断ガラスと長ガラスとの混合物を含む複合射出成形GF−PET−PBTブレンドにさらに結合して、車両の構築に適した硬質な構造部品を形成することができる。これらのハイブリッド部品は、Eコート塗装などの塗装に使用される高温(180〜220℃)オーブンに曝露された後(1〜6時間)でもそれらの形状を保持することができる。
Claims (15)
- ポリエステル組成物を含む製造物品であって、前記物品が、ASTM D3418に従って示差走査熱量測定によって一回目の加熱時に1分当たり20℃の加熱速度で測定したときに、
第1の結晶溶融温度および第2の結晶溶融温度が各々独立に200〜290℃である、少なくとも2つの異なる結晶溶融温度と;
各々独立に少なくとも3J/gである第1の融解熱および第2の融解熱であって、好ましくは前記第1の融解熱の前記第2の融解熱に対する比率が1:5〜5:1である、第1の融解熱および第2の融解熱と;を含み、
前記ポリエステル組成物が、
前記ポリエステル組成物の総重量に基づいて、重量で20ppm以上のリン含有量を有する第1のポリエステルと、
第2のポリエステルと、
前記ポリエステル組成物の総重量に基づいて5〜50重量パーセントの、5〜25マイクロメートルの直径を有する複数の繊維と、を含む、製造物品。 - ASTM D3418に従って示差走査熱量測定によって一回目の冷却時に1分当たり20℃の冷却速度で測定したときに、
第1の結晶化温度および第2の結晶化温度が各々独立に180〜290℃であり、好ましくは前記第2の結晶化温度が225〜290℃であり、前記第1の結晶化温度より大きい、少なくとも2つの異なる結晶化温度と;
各々独立に−3J/g以下である第1の結晶化熱および第2の結晶化熱であって、好ましくは前記第1の結晶化熱の前記第2の結晶化熱に対する比率が1:5〜5:1である、第1の結晶化熱および第2の結晶化熱と;をさらに含む、請求項1に記載の物品。 - ASTM D638に従って23℃で1分当たり50mmのクロスヘッド速度で測定したときに、少なくとも6,000MPa、好ましくは6,000〜24,000MPaの引張り弾性率;
ASTM D638に従って23℃で1分当たり50mmのクロスヘッド速度で測定したときに、少なくとも70MPa、好ましくは70〜180MPaの引張り降伏強さ;
ASTM D648に従って0.45MPaで測定したときに、少なくとも180℃、好ましくは180〜220℃の加熱撓み温度;および
ASTM D1238に従って265℃で6分間2.16kgの荷重で測定したときに、10〜80cm3/10分のメルトボリュームフローレイト
のうちの1つまたは複数を有する、請求項1または2に記載の物品。 - 前記第1のポリエステルが、
ポリスチレン標準を使用するゲル浸透クロマトグラフィーによって測定したときに、1モル当たり15,000〜80,000グラムの重量平均分子量;
1キログラム当たり20ミリモル当量超のカルボキシルCOOH末端基含有量;
1キログラム当たり20ミリモル当量超のヒドロキシOH末端基含有量;
少なくとも1.3:1のヒドロキシ末端基のカルボキシル末端基に対する比率;および
重量で10ppm超であるが重量で200ppm未満の金属含有量を有し、前記金属が、チタン、ジルコニウム、亜鉛、アンチモン、ゲルマニウム、コバルト、スズ、またはそれらの組み合わせである、請求項1〜3のいずれか一項に記載の物品。 - 前記ポリエステル組成物が、
前記ポリエステル組成物の総重量に基づいて、10〜60重量パーセント、好ましくは20〜50重量パーセントの第1のポリエステルであって、ポリ(エチレンテレフタレート)を含む第1のポリエステルと;
前記ポリエステル組成物の総重量に基づいて、10〜85重量パーセント、好ましくは20〜60重量パーセントの第2のポリエステルであって、ポリ(ブチレンテレフタレート)を含む第2のポリエステルと;を含み、
好ましくは、前記第2のポリエステルが、第1のポリ(ブチレンテレフタレート)および第2のポリ(ブチレンテレフタレート)を含み、より好ましくは、
前記第1のポリ(ブチレンテレフタレート)の固有粘度が前記第2のポリ(ブチレンテレフタレート)の固有粘度と異なるか;または
前記第1のポリ(ブチレンテレフタレート)の重量平均分子量が前記第2のポリ(ブチレンテレフタレート)の重量平均分子量と異なるか;または
前記固有粘度と前記重量平均分子量が両方とも異なる、請求項1〜4のいずれか一項に記載の物品。 - 前記複数の繊維が、複数の細断ガラス繊維、長ガラス繊維、ガラスフィラメント、ガラス繊維織物、炭素繊維、炭素繊維織物、セラミック繊維、またはそれらの組み合わせを含む、請求項1〜5のいずれか一項に記載の物品。
- 前記ポリエステル組成物が、
前記ポリエステル組成物の総重量に基づいて0.01〜0.5重量パーセントの安定剤、好ましくは、0.01〜0.3重量パーセントのヒンダードフェノール、ホスファイト、ホスホナイト、チオエステル、またはそれらの組み合わせ;
前記ポリエステル組成物の総重量に基づいて0.01〜8重量パーセントの核剤、好ましくは、0.05〜5重量パーセントのタルク、シリカ、シロキサン、粘土、アルカリカルボン酸塩、またはそれらの組み合わせ;
前記ポリエステル組成物の総重量に基づいて0.01〜2重量パーセントの離型剤、好ましくは、0.1〜0.8重量パーセントの脂肪酸エステル、ワックス、ポリオレフィン、またはそれらの組み合わせ;および
前記ポリエステル組成物の総重量に基づいて0〜5重量パーセントの着色剤、好ましくは、0.1〜5重量パーセントのカーボンブラック、染料、顔料、またはそれらの組み合わせ
をさらに含む、請求項1〜6のいずれか一項に記載の物品。 - 前記ポリエステル組成物が、前記ポリエステル組成物の総重量に基づいて1〜30重量パーセントの衝撃改質剤;
好ましくは、1〜15重量パーセントのアルキル(メタ)アクリレートコポリマー、(メタ)アクリル酸エステル−ブタジエン−スチレン、アクリロニトリル−ブタジエン−スチレン、スチレン−ブタジエン、スチレン−エチレン−ブチレン−スチレン、ポリ(エーテルエステル)ブロックコポリマー、ポリエチレン−αオレフィンコポリマー、スチレン−イソプレン−スチレントリブロックコポリマー、またはそれらの組み合わせ
をさらに含む、請求項1〜7のいずれか一項に記載の物品。 - 請求項1〜8のいずれか一項に記載の物品を含む、ポリエステルプリプレグ。
- 請求項9に記載のポリエステルプリプレグを圧密化することによって生成されるポリエステル複合材料であって、好ましくは、少なくとも2層、より好ましくは2〜100層の前記ポリエステルプリプレグを熱および圧力下で圧密化することによって生成される積層体の形態の、ポリエステル複合材料。
- 前記プリプレグ層が、連続一方向繊維強化ポリエステルテープの形態である、請求項10に記載のポリエステル複合材料。
- 前記連続一方向繊維強化ポリエステルテープが同じ方向に配向され、前記複合材料が、
ASTM D7264に従って測定したとき、独立に20MPa超、好ましくは20〜60MPaである、縦方向および横方向の曲げ強さであって、前記縦方向の曲げ強さの前記横方向の曲げ強さに対する比率が2:1未満である、曲げ強さ;
ASTM D7264に従って測定したとき、独立に200GPa超、好ましくは200〜600GPaである、縦方向および横方向の曲げ弾性率であって、前記縦方向の曲げ弾性率の前記横方向の曲げ弾性率に対する比率が2:1未満である、曲げ弾性率;
15〜80%、好ましくは25%〜70%の繊維体積分率;ならびに
ASTM D792に従って測定したとき、1.3〜2.4g/cm3、好ましくは1.4〜2.2g/cm3の平均密度
のうちの1つまたは複数を有する、請求項11に記載のポリエステル複合材料。 - 請求項1〜8のいずれか一項に記載の物品を含むポリマー強化材であって、六角形の幾何学的形状を有する中空の多室構造を有する、ポリマー強化材。
- 主軸を有するチャンネルを画定する壁を含む中空部材と;
請求項13に記載のポリマー強化材と;を含み、
前記ポリマー強化材が、前記チャンネル内に位置しており、
前記中空の多室構造が、前記主軸に対して垂直または平行に配向される二次チャンネルを含む、構造体。 - 請求項10〜12のいずれか一項に記載のポリエステル複合材料を製造する方法であって、
前記第1のポリエステルと前記第2のポリエステルとを含むブレンドで、複数の繊維を含む基材を被覆して、被覆された基材を形成すること;
前記被覆された基材を第1の温度で加熱してポリエステルプリプレグを形成すること;
複数のポリエステルプリプレグを層状に積み重ねること;および
前記複数のポリエステルプリプレグを第2の温度で圧力下で加熱して前記ポリエステル複合材料を形成すること
を含む、方法。
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CN115190841A (zh) * | 2019-12-12 | 2022-10-14 | 尼蓝宝股份有限公司 | 功能化纺织品材料的集合体及其使用方法 |
WO2021199842A1 (ja) | 2020-03-31 | 2021-10-07 | 東レ株式会社 | ポリエステル樹脂組成物、成形品、および複合成形品 |
US20230303827A1 (en) * | 2020-08-11 | 2023-09-28 | Toyobo Co., Ltd. | Inorganic material-reinforced thermoplastic polyester resin composition and method for producing same |
WO2023086857A1 (en) * | 2021-11-12 | 2023-05-19 | Essentium Ipco, Llc | Polyphenylene sulfide blends for three-dimensional printer filament |
WO2023126207A1 (en) * | 2021-12-28 | 2023-07-06 | Sabic Global Technologies B.V. | Glass fiber-reinforced thermoplastic polymer composition |
WO2023244278A1 (en) * | 2022-06-12 | 2023-12-21 | Cnpc Usa Corporation | Preparation of degradable polyester composites and use thereof |
KR102656657B1 (ko) * | 2023-04-12 | 2024-04-11 | 에스케이케미칼 주식회사 | 폴리에스테르 연신 필름 및 이의 제조방법 |
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US20210054155A1 (en) | 2021-02-25 |
CN112135866A (zh) | 2020-12-25 |
EP3790925A1 (en) | 2021-03-17 |
EP3790925B1 (en) | 2024-01-03 |
KR20210008511A (ko) | 2021-01-22 |
WO2019217680A1 (en) | 2019-11-14 |
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